CN107195767A - A kind of five yuan of N-type thermoelectric materials and preparation method thereof - Google Patents
A kind of five yuan of N-type thermoelectric materials and preparation method thereof Download PDFInfo
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- CN107195767A CN107195767A CN201710431363.4A CN201710431363A CN107195767A CN 107195767 A CN107195767 A CN 107195767A CN 201710431363 A CN201710431363 A CN 201710431363A CN 107195767 A CN107195767 A CN 107195767A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
Abstract
The invention discloses a kind of five yuan of N-type thermoelectric materials, its formula is Bi2‑x‑yInxSyTe3‑zSez；Wherein 0.01≤x≤0.20,0.01≤y≤0.15,0.10≤z≤0.30；Mixed the invention also discloses the preparation method of thermoelectric material, including powder：Bi, Te, Se, In and S elemental powders are taken, batch mixing is carried out using ball mill or batch mixer, obtains mixed powder；Alloy melting：Mixed powder is fitted into boiler tube, chemical vapor deposition is carried out in boiler tube, or mixed powder is fitted into the quartz ampoule that one end has been sealed, quartz ampoule load facility is subjected to melting, the alloy pig of five yuan of N-type thermoelectric materials is obtained；Averagely ZT values are high and do not raise and decay with temperature, and temperature in use scope is wide, and production technology, equipment are simple, reduce the unit cost of thermo-electric generation, solve the technical barrier of less than 200 DEG C of low-temperature waste heat recovery power generating industry.
Description
Technical field
The present invention relates to a kind of five yuan of N-type thermoelectric materials and preparation method thereof, belong to new energy materialses and its technology of preparing
Field.
Background technology
In recent years, population is skyrocketed through and industrial fast development, fossil fuel exhaustive exploitation, and the energy and environmental problem are all the more
Highlight, energy crisis and environmental crisis have caused various countries to pay close attention to.However, there are about 70% in the energy that the whole world is consumed every year with used heat
Form be wasted, if these used heat effectively can be recycled, the problem of greatly alleviating energy shortage.
Thermoelectric material can directly convert thermal energy into electric energy, with without drive disk assembly, small volume, noiseless, pollution-free and good reliability
The advantages of, recycled in automobile waste heat, have huge application in terms of industrial afterheat power generation and solar energy optical-thermal compound power-generating
Prospect.
The thermoelectricity capability of thermoelectric material is by dimensionless thermoelectric figure of merit ZT (ZT=α2σ T/ κ, wherein α are that Seebeck coefficient, σ are
Electrical conductivity, κ are thermal conductivity factor, are made up of lattice thermal conductivity factor and electronics thermal conductivity factor two parts, T is absolute temperature, α2σ is referred to as
Power factor) determine.ZT is bigger, and the conversion efficiency of thermoelectric of material is higher.By aforesaid equation, institute is obvious, turns to improve thermoelectricity
The performance of conversion materials is, it is necessary to improve Seebeck coefficient α and electrical conductivity or reduction thermal conductivity factor κ.But Seebeck coefficient, σ conductances
But there is extremely complex contact and influence between rate and thermal conductivity factor three.The existing method for improving electrical conductivity, such as by applying
The mode of main doping is adulterated the donor impurity of the halogen compounds class such as Se or TeI4, CuI, AgI, CuBr in n type material, or
By way of acceptor doping, the metallic element acceptor impurities such as Sb, Al, Cu, Ag that adulterated in P-type material are dense to increase carrier
Degree and mobility, although electrical conductivity can be effectively improved, but also cause the heat transport of carrier to significantly increase, make material conducts heat system
Number is also significantly increased, meanwhile, high carrier concentration and mobility will cause significantly reducing for Seebeck coefficient.Conversely, mesh
The scheme of preceding compacting thermal conductivity coefficient, such as doping, material nano are micronized etc., although can obtain higher Seebeck coefficient and compared with
Low thermal conductivity factor, but electrical conductivity is all damaged in various degree, ultimately result in ZT values relatively low；Material nano is micronized in addition needs water
Heat, solvent thermal reaction equipment, electrochemical deposition, melt get rid of the equipment such as band, MOCVD or molecular beam epitaxy, subsequently also need Vacuum Heat
Pressure sintering or SPS sintering, equipment investment is expensive, operating cost is high, it is impossible to continuously and stably produced in enormous quantities, main at present
Apply in scientific research field.
The commercial low-temperature space thermoelectric material of existing market sale is Bi2Te3Based alloy, in Bi2Te3On the basis of adulterate acceptor
Sb or alms giver Se, TeI4Etc. ternary or quaternary solid solution alloy is formed, its electrical conductivity is in 0.8-1.3*105Sm-1Between, Seebeck
Coefficient is 160-220 μ V/K, and thermal conductivity factor is 1.4-2.4Wm-1K-1, its average ZT value is 0.8 or so, and conversion efficiency of thermoelectric is only
For 1% or so, its subject matter is that thermal conductivity factor is higher, and as temperature is raised, resistivity of material and heat conduction are raised rapidly,
Cause material ZT values with the rapid decay of temperature rise, when having a strong impact on thermoelectricity capability and the application effect, particularly high temperature of material
Application.And in thermoelectric material field, the ZT values of material often lift 0.1, it is required for substantial amounts of R＆D fund and personnel to put into.
The content of the invention
In order to overcome the deficiencies in the prior art, first purpose of the invention is to provide a kind of five yuan of N-type thermoelectric materials,
Five yuan of N-type thermoelectric materials have low thermal conductivity, average ZT values are high and do not raise and decay with temperature, temperature in use scope
Width, production technology, equipment are simple, reduce the unit cost of thermo-electric generation, solve (less than 200 DEG C) of low-temperature waste heat and reclaim hair
The technical barrier of electric industrialization.
Second object of the present invention is to provide a kind of preparation method of above-mentioned five yuan of N-type thermoelectric materials, passes through the system
Preparation Method can realize single more than furnace output 80kg high-volume industrial production.
Realizing first purpose of the present invention can be reached by adopting the following technical scheme that：A kind of five yuan of N-type thermoelectricity materials
Material, its formula is Bi2-x-yInxSyTe3-zSez；Wherein 0.01≤x≤0.20,0.01≤y≤0.15,0.10≤z≤0.30.
Further, the active ingredient in five yuan of N-type thermoelectric materials is by Bi2S3、Bi2Te3、Bi2Se3、In2S3、In2Te3、
In2Se3With SSeTe compositions.
Further, wherein Bi, Te, Se, In and S mole percent are respectively：33-39.6%, 54-58%, 2-
6%th, 0.2-4% and 0.2-3%.
Realize that second object of the present invention can reach by adopting the following technical scheme that：A kind of five yuan as described above
The preparation method of N-type thermoelectric material, including：
Powder blend step：Bi, Te, Se, In and S elemental powders are taken, is fitted into vacuum ball grinder and vacuumizes, then
Batch mixing is carried out using ball mill；
Or, Bi, Te, Se, In and S elemental powders are taken, load in batch mixing machine jar body, be passed through inert gas shielding, then
Batch mixing is carried out using batch mixer；
Obtain mixed powder；
Alloy melting step：Mixed powder is fitted into boiler tube, 10 are evacuated to-2Pa, is heated to 700-1100 DEG C, makes original
Expect powder body melting vaporization, chemical vapor deposition carried out in boiler tube, the reaction time is 20-30h, reaction terminates rear natural cooling,
Obtain the alloy pig of five yuan of N-type thermoelectric materials；Or, mixed powder is fitted into the quartz ampoule that one end has been sealed, it is evacuated to
0.1-20pa and melt sealing；Packaged quartz ampoule load facility is subjected to melting, smelting temperature is 600-800 DEG C, when
Between be 20-50h, reaction terminate rear natural cooling, obtain the alloy pig of five yuan of N-type thermoelectric materials.
Further, in powder blend step, the purity of Bi, Te, Se, In and S elemental powders is 4-5N.
Further, in powder blend step, the mesh number of Bi, Te, Se, In and S elemental powders is 60-325 mesh.
Further, in powder blend step, the vacuum vacuumized is≤20Pa.
Further, in powder blend step, inert gas is argon gas or nitrogen.
Further, in powder blend step, the rotating speed of ball mill or batch mixer is 20-50r/min, mixing time
10-30h。
Further, in alloy melting step, a diameter of 20-45mm of quartz ampoule, length 200-1000mm；Will be packaged
Quartz ampoule feeding area smelting furnace carry out zone refining, or be put into resistance-heated furnace and carry out melting.
The design principle of the present invention is as follows：
The present invention is directed to tradition Bi2Te3-mSemThe deficiency of ternary doping alloy N-type thermoelectric material, by adding certain proportion
Two kinds of elements of In, S replace part Bi elements, constitute five yuan of rock-steady structure type solid solution alloy thermoelectric materials.With traditional thermoelectricity
Material doped method of modifying compares, and (adulterate the acceptor impurity such as Sb, Al, Cu, Ag or in N-type material such as in p-type thermoelectric material
Adulterate Se, TeI in material4Etc. donor impurities such as halogen compounds) have dramatically different, S is that atomic radius is much smaller than Bi, Te
And Se, the big nonmetalloid of electronegativity.And In is the atomic radius metallic element smaller than Bi, and have again in terms of orbital hybridization
The effect wanted.Element S can electronically form electron localized state, in material with trapping material because of its larger electronegativity with
Middle formation electron trap, so as to maintain carrier concentration in material within the specific limits, to make material that there is higher Sai Beike systems
Number and electrical conductivity simultaneously reduce electronics thermal conductivity factor.Element In and S atomic radius or coordination mode differed with Bi, Te and Se compared with
Greatly, Bi therefore in material2S3、Bi2Te3、Bi2Se3、In2S3、In2Te3、In2Se3The lattice constant of these structural motifs has one
Fixed difference, therefore a large amount of dangling bonds can be produced in these structural motif interfaces, cause lattice mismatch, scattering is played to phonon
Effect, so as to effectively reduce the lattice thermal conductivity factor of material.Compared with prior art, the beneficial effects of the present invention are：
1st, five yuan of N-type thermoelectric materials of the invention have that low thermal conductivity, thermoelectricity capability be excellent, conversion efficiency of thermoelectric is high
Feature；
2nd, five yuan of N-type thermoelectric materials of the invention have highly stable performance and operational characteristic, are adapted to powder metallurgy and burn
Moulding process is tied, therefore by the preparation method of the application, high-volume industrial production can be achieved.
Brief description of the drawings
Fig. 1 is the curve map of thermal conductivity factor；
Fig. 2 is the curve map of Seebeck coefficient；
Fig. 3 is the curve map of resistivity；
Fig. 4 is thermoelectric figure of merit ZT curve map；
Fig. 5 is the alloy that the melting of embodiment 1 is obtained；
Fig. 6 is the block that embodiment 2 is made with alloy；
Fig. 7 is the alloy that the melting of embodiment 1 is obtained；
Fig. 8 is the block that embodiment 2 is made with alloy；
Fig. 9 is Bi1.75In0.12S0.13Te2.85Se0.15The micro- crystalline phase figure of thermoelectric material.
Embodiment
Below, with reference to accompanying drawing and embodiment, the present invention is described further：
A kind of five yuan of N-type thermoelectric materials, it is characterised in that its formula is Bi2-x-yInxSyTe3-zSez；Wherein 0.01≤x≤
0.20,0.01≤y≤0.15,0.10≤z≤0.30, i.e. Bi, Te, Se, In and S mole percent is respectively：33-
39.6%th, 54-58%, 2-6%, 0.2-4% and 0.2-3%.
Five yuan of N-type thermoelectric materials of the present invention are a kind of functional materials that can mutually change heat energy and electric energy.It can answer
It is wild for more multi-field, such as low-temperature space (- 200 DEG C of room temperature) heat energy (industrial exhaust heat, used heat, underground heat and solar energy optical-thermal) generating
Outside, the small-sized electric generating apparatus that outlying district or special industry are used.For remote space probe, radio isotope is supplied
Heat thermoelectric generator be unique electric power system, by be successfully applied to NASA transmitting " traveller No. one " and
On spacecrafts such as " Galileo Mars probes ".Thermoelectric power generation is used equally for using the nature temperature difference and industrial exhaust heat, used heat, it
The uncontamination energy that can exist using nature, or industrial exhaust heat Waste Heat Recovery is converted into electric energy, improve using energy source effect
Rate, with good synthesis social benefit.The thermoelectric cooler being made using peltier effect has mechanical compression refrigeration machine difficult
With the advantage matched in excellence or beauty：Size is small, light weight, without any mechanical rotation part, work noiseless, no liquid or gaseous medium, because
The problem of pollution environment is not present in this, can be achieved accurate temperature controlling, and fast response time, device service life is long.In addition with electronics
The development of industry, the micro element prepared using thermoelectric material is used to prepare micro power, microcell cooling, the pole of optical communication laser two
The thermoregulating system of pipe and infrared ray sensor, has expanded the application field of thermoelectric material significantly.Five yuan of N-type thermoelectric materials of the invention
Mean coefficient of heat conductivity be less than 0.7W/mK, only Traditional dopant type binary, ternary, quaternary Bi2Te3The 30%- of class material
50%, material Seebeck coefficient and electrical conductivity are still maintained in preferable scope, and average ZT values are more than 1, ZT values not with temperature liter
High and decay, thermoelectricity capability improves 20%-40%, and temperature in use scope is wide.
In fact, the element in five yuan of N-type thermoelectric materials is present in the form of compound, it is by Bi2S3、Bi2Te3、
Bi2Se3、In2S3、In2Te3、In2Se3It is solid solution alloy with SSeTe compositions；Bi2S3、Bi2Te3、Bi2Se3、In2S3、In2Te3、
In2Se3Construction unit lattice parameter it is different, their interface can produce lattice mismatch, cause shape inside solid solution alloy
Into a large amount of dangling bonds.Dangling bonds can play significant strong scattering to the transmission of phonon during lattice vibrations and act on, so as to have
The lattice thermal conductivity factor of the reduction material of effect.
The preparation method of five yuan of N-type thermoelectric materials, including：
Powder blend step：Bi, Te, Se, In and S elemental powders are taken, is fitted into vacuum ball grinder and vacuumizes, then
Batch mixing is carried out using ball mill；
Or, Bi, Te, Se, In and S elemental powders are taken, load in batch mixing machine jar body, be passed through inert gas shielding, then
Batch mixing is carried out using batch mixer；
Obtain mixed powder；
Alloy melting step：Mixed powder is fitted into boiler tube, 10 are evacuated to-2Pa, is heated to 700-1100 DEG C, makes original
Expect powder body melting vaporization, chemical vapor deposition carried out in boiler tube, the reaction time is 20-30h, reaction terminates rear natural cooling,
Obtain the alloy pig of five yuan of N-type thermoelectric materials；
Or, mixed powder is fitted into the quartz ampoule that one end has been sealed, it is evacuated to 0.1-20pa and melts sealing；
Packaged quartz ampoule load facility is subjected to melting, smelting temperature is 600-800 DEG C, and the time is 20-50h, after reaction terminates
Natural cooling, obtains the alloy pig of five yuan of N-type thermoelectric materials.
As preferred embodiment, the purity of Bi, Te, Se, In and S elemental powders is 4-5N.
As preferred embodiment, in powder blend step, the mesh number of Bi, Te, Se, In and S elemental powders is 60-
325 mesh.
As preferred embodiment, in powder blend step, the vacuum vacuumized is≤20Pa.
As preferred embodiment, in powder blend step, inert gas is argon gas or nitrogen.
As preferred embodiment, in powder blend step, the rotating speed of ball mill or batch mixer is 20-50r/min,
Mixing time 10-30h.
As preferred embodiment, in alloy melting step, a diameter of 20-45mm of quartz ampoule, length 200-
1000mm；Packaged quartz ampoule feeding area smelting furnace is subjected to zone refining, or is put into resistance-heated furnace and carries out melting.
Embodiment 1：
Formula is Bi1.75In0.12S0.13Te2.85Se0.15Five yuan of N-type thermoelectric materials preparation method, including：
Powder blend step：It is by Bi, Te, Se, In and S molar fraction：35%th, 2.4%, 2.6%, 57% and 3%
Ratio weigh purity is 4N, mesh number is 300 mesh Bi, Te, Se, In and S elemental powders, be fitted into vacuum ball grinder and with
Vacuum is vacuumized for 6Pa, and batch mixing is then carried out under conditions of rotating speed 40r/min, mixing time 25h using ball mill；
To mixed powder；
Alloy melting step：Mixed powder is fitted into boiler tube, 10 are evacuated to-2Pa, is heated to 800 DEG C, makes raw material powder
Body melting vaporization, carries out chemical vapor deposition, the reaction time is 23h, reaction terminates rear natural cooling, obtains five yuan in boiler tube
The alloy pig of N-type thermoelectric material.
3.79%Bi of the embodiment 1 containing mass percent2S3, 79.34%Bi2Te, 4.37%Bi2Se3, 0.26%InS,
5.44%InTe, 0.3%InSe and 6.5%SSeTe.
Embodiment 2：
Formula is Bi1.8In0.1S0.1Te2.8Se0.2Five yuan of N-type thermoelectric materials preparation method, including：
Powder blend step：The molar fraction for taking Bi, Te, Se, In and S is：36%th, 2%, 2%, 56% and 4% ratio
Example weighs purity is 5N, mesh number is 250 mesh Bi, Te, Se, In and S elemental powders, loads in batch mixing machine jar body, is passed through nitrogen
Gas shielded, then carries out batch mixing using batch mixer under conditions of 35r/min, mixing time 28h；Obtain mixed powder；
Alloy melting step：A diameter of 35mm is taken, mixed powder is loaded one end and sealed by length 800mm quartz ampoule
In the quartz ampoule of mouth, it is evacuated to 10pa and melts sealing；Packaged quartz ampoule feeding area smelting furnace is subjected to region
Melting, smelting temperature is 750 DEG C, and the time is 42h, and reaction terminates rear natural cooling, obtains the alloy of five yuan of N-type thermoelectric materials
Ingot.
3%Bi of the embodiment 2 containing mass percent2S3, 81%Bi2Te, 6%Bi2Se3, 0.17%InS, 4.5%
InTe, 0.33%InSe and 5%SSeTe.
Examples 1 and 2 are tested：
Heat conduction coefficient tester device is：U.S. TA, FL4010 laser heat conducting instrument；Germany is resistance to speed, DSC-200F3.
The resistivity measurement method of material is at room temperature：Material is prepared into block using cold pressing-sintering processing, using four
Probe resistance rate tester (Suzhou lattice, ST2722) is tested.
Seebeck coefficient, resistance (conductance) rate test commission third party testing agency under material different temperatures：The micro- spectrum in Shanghai
Chemical Engineering Technology and Guangzhouization connection are tested, and tester is respectively that German Lindsay this and Japan ZEM-3 Seebeck coefficients is tested
Instrument.
The curve map of the thermal conductivity factor of material obtained by test is as shown in figure 1, curve map such as Fig. 2 institutes of Seebeck coefficient
Show, the curve map of resistivity is as shown in figure 3, thermoelectric figure of merit ZT curve map is as shown in Figure 4；
The alloy of embodiment 1 that batch melting is obtained is as shown in figure 5, using cold pressing-sintering (powder metallurgy) mode by alloy
The block being prepared into is as shown in Figure 6；The 2-in-1 gold of embodiment is as shown in fig. 7, using cold pressing-sintering (powder metallurgy) mode by alloy
The block being prepared into is as shown in figure 8, embodiment 1,2 can realize batch production.
Test data is as shown in tables 1 and 2：
The test result of the embodiment 1 of form 1
The test result of the embodiment 2 of form 2
Fig. 9 is the Bi of embodiment 11.75In0.12S0.13Te2.85Se0.15The micro- crystalline phase figure of thermoelectric material, tester is wide
The HOK-0731 type metallographic microscopes of state city sea Cohan automation equipment Co., Ltd, the alloy for taking a small pieces melted is used
1500 mesh abrasive paper for metallograph are polished surface, and the camera system carried with instrument claps crystalline phase image of drawing materials.
For those skilled in the art, technical scheme that can be as described above and design, make other each
It is kind corresponding to change and deform, and all these change and deformation should all belong to the protection model of the claims in the present invention
Within enclosing.
Claims (10)
1. a kind of five yuan of N-type thermoelectric materials, it is characterised in that its formula is Bi2-x-yInxSyTe3-zSez；Wherein 0.01≤x≤
0.20,0.01≤y≤0.15,0.10≤z≤0.30.
2. five yuan of N-type thermoelectric materials as claimed in claim 1, it is characterised in that effective in five yuan of N-type thermoelectric materials
Composition is by Bi2S3、Bi2Te3、Bi2Se3、In2S3、In2Te3、In2Se3With SSeTe compositions.
3. five yuan of N-type thermoelectric materials as claimed in claim 1, it is characterised in that wherein moles the hundred of Bi, Te, Se, In and S
Fraction is respectively：33-39.6%, 54-58%, 2-6%, 0.2-4% and 0.2-3%.
4. a kind of preparation method of five yuan of N-type thermoelectric materials as claimed in claim 1, it is characterised in that the preparation method bag
Include：
Powder blend step：Bi, Te, Se, In and S elemental powders are taken, is fitted into vacuum ball grinder and vacuumizes, then utilize
Ball mill carries out batch mixing；
Or, Bi, Te, Se, In and S elemental powders are taken, load in batch mixing machine jar body, be passed through inert gas shielding, then utilize
Batch mixer carries out batch mixing；
Obtain mixed powder；
Alloy melting step：Mixed powder is fitted into boiler tube, 10 are evacuated to-2Pa, is heated to 700-1100 DEG C, makes raw material powder
Body melting vaporization, carries out chemical vapor deposition, the reaction time is 20-30h, reaction terminates rear natural cooling, obtains in boiler tube
The alloy pig of five yuan of N-type thermoelectric materials；
Or, mixed powder is fitted into the quartz ampoule that one end has been sealed, it is evacuated to 0.1-20pa and melts sealing；Will envelope
The quartz ampoule load facility installed carries out melting, and smelting temperature is 600-800 DEG C, and the time is 20-50h, and reaction is natural after terminating
Cooling, obtains the alloy pig of five yuan of N-type thermoelectric materials.
5. the preparation method of five yuan of N-type thermoelectric materials as claimed in claim 4, it is characterised in that in powder blend step, institute
The purity for stating Bi, Te, Se, In and S elemental powders is 4-5N.
6. the preparation method of five yuan of N-type thermoelectric materials as claimed in claim 4, it is characterised in that in powder blend step, institute
The mesh number for stating Bi, Te, Se, In and S elemental powders is 60-325 mesh.
7. the preparation method of five yuan of N-type thermoelectric materials as claimed in claim 4, it is characterised in that in powder blend step, take out
The vacuum of vacuum is≤20Pa.
8. the preparation method of five yuan of N-type thermoelectric materials as claimed in claim 4, it is characterised in that in powder blend step, institute
Inert gas is stated for argon gas or nitrogen.
9. the preparation method of five yuan of N-type thermoelectric materials as claimed in claim 4, it is characterised in that in powder blend step, institute
The rotating speed for stating ball mill or batch mixer is 20-50r/min, mixing time 10-30h.
10. the preparation method of five yuan of N-type thermoelectric materials as claimed in claim 4, it is characterised in that in alloy melting step,
A diameter of 20-45mm of quartz ampoule, length 200-1000mm；Packaged quartz ampoule feeding area smelting furnace is carried out into region to melt
Refining, or be put into resistance-heated furnace and carry out melting.
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| CN111244257A (en) * | 2020-01-20 | 2020-06-05 | 昆明理工大学 | Bi-Sb-Te-Se-S quinary high-entropy alloy and preparation method thereof |
| CN111304492A (en) * | 2020-03-12 | 2020-06-19 | 中南大学 | Low-temperature n-type thermoelectric material and preparation method thereof |
| CN112397634A (en) * | 2020-11-16 | 2021-02-23 | 昆明理工大学 | Method for improving performance of Bi-Sb-Te-based thermoelectric material |
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| CN108649115A (en) * | 2018-05-10 | 2018-10-12 | 广东雷子克热电工程技术有限公司 | Five yuan based on the sintering phase transformation of crystal topological realization powder metallurgy are N-shaped thermoelectric material and preparation method |
| WO2019214158A1 (en) * | 2018-05-10 | 2019-11-14 | 广东雷子克热电工程技术有限公司 | Five-elements n-type thermoelectric material realizing powder alloy sintering phase transformation based on crystal topology, and preparation method |
| GB2589238A (en) * | 2018-05-10 | 2021-05-26 | Leizip Guangdong Thermoelectric Tech Co Ltd | Five-elements n-type thermoelectric material realizing powder allow sintering phase transformation based on crystal topology, and preparation method |
| GB2589238B (en) * | 2018-05-10 | 2022-05-11 | Leizig Guangdong Thermoelectric Tech Co Ltd | Five-elements n-type thermoelectric material realizing powder alloy sintering phase transformation based on crystal topology, and preparation method |
| CN111244257A (en) * | 2020-01-20 | 2020-06-05 | 昆明理工大学 | Bi-Sb-Te-Se-S quinary high-entropy alloy and preparation method thereof |
| CN111244257B (en) * | 2020-01-20 | 2022-08-05 | 昆明理工大学 | Bi-Sb-Te-Se-S quinary high-entropy alloy and preparation method thereof |
| CN111304492A (en) * | 2020-03-12 | 2020-06-19 | 中南大学 | Low-temperature n-type thermoelectric material and preparation method thereof |
| CN111304492B (en) * | 2020-03-12 | 2021-07-06 | 中南大学 | Low-temperature n-type thermoelectric material and preparation method thereof |
| CN112397634A (en) * | 2020-11-16 | 2021-02-23 | 昆明理工大学 | Method for improving performance of Bi-Sb-Te-based thermoelectric material |
| CN112397634B (en) * | 2020-11-16 | 2023-02-28 | 昆明理工大学 | Method for improving performance of Bi-Sb-Te-based thermoelectric material |
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| CN107195767B (en) | 2019-08-23 |
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Denomination of invention: A five element n-type thermoelectric material and its preparation method Effective date of registration: 20210607 Granted publication date: 20190823 Pledgee: Bank of China Limited Guangzhou Development Zone Branch Pledgor: Leizig (Guangdong) Thermoelectric Technologies Co.,Ltd. Registration number: Y2021980004454 |